1. Field of the Invention
The present invention relates to a method and apparatus for the production of highly pure ruthenium and ruthenium dioxide.
2. Description of the Related Art and General Background
A member of the platinum group, ruthenium occurs naturally with other members of the platinum group in ores found in Russia's Ural mountains, North and South America, and particularly, South Africa. It is also found along with other platinum metals in small but commercial quantities in both the pentlandite of the Sudbury, Ontario, nickel-mining region, and in the pyroxinite deposits of South Africa. Commercially, ruthenium may be isolated from the other platinum metals through several complex chemical processes, the final stage of which generally includes the hydrogen reduction of ammonium ruthenium chloride or nitrosylruthenium chloride, to produce ruthenium metal powder.
Ruthenium, a hard, white metal, is one of the most effective hardeners for platinum and palladium and is typically alloyed with these metals to produce electrical contacts for severe wear resistance. There have also been reports that a ruthenium alloy, specifically a ruthenium-molybdenum alloy, exhibits superconductivity at 10.6° K. It has also been reported that the corrosion resistance of titanium can be improved over 100 times by adding as little as 0.1% ruthenium. Ruthenium is also a versatile catalyst and is frequently used in petrochemical and other industrial processes to remove H2S.
One method for extracting ruthenium is disclosed in U.S. Pat. No. 3,997,337 (“the '337 patent”). The '337 patent included a discussion of both earlier methods for the separation and purification of precious metals, including ruthenium, from a concentrate of by-metals and the improved method taught by the patent. The improvement disclosed in the '337 patent for the separation and purification of precious metals, including ruthenium, from a concentrate of by-metals comprised heating the concentrate to a temperature between 1100° C. and 1500° C., preferably at about 1300° C., in a gaseous stream which comprises oxygen. This heating step is continued for a period sufficient to ensure quantitative removal of one or more of lead, arsenic, silver, bismuth and/or tellurium and the oxidation of ruthenium, rhodium and iridium. The referenced by-metal concentrate is obtained as a by-product of the separation of platinum, palladium, and gold from an ore or other mixed source.
In the previous process, the by-metal concentrate was fused with potassium bisulphate (KHSO4) to convert the rhodium to the water-soluble sulphate, Rh2(SO4)3, which can be removed by washing. The remaining residue was then subjected to a sodium peroxide (Na2O2) fusion to convert the ruthenium and osmium to water soluble sodium salts of their oxo-anions (e.g. RuO42− and Os42− respectively) and to convert the iridium to an acid soluble hydrous oxide (probably IrO2.nH2O). The ruthenium and osmium were then separated from the iridium by treating the sodium peroxide melt with water to form a precipitate, and treating the precipitate with hydrochloric acid to dissolve the iridium. The ruthenium and osmium were then normally purified by a collective chlorine distillation, followed by a nitric acid distillation for osmium. The rhodium is treated for the removal of impurities such as palladium, tellurium and other base metals that are also rendered soluble by the KHSO4 fusion. The iridium has to be separated from large quantities of lead and other impurities present in the concentrate which have been rendered soluble by the sodium peroxide (Na2O2) fusion. As can be appreciated, this method used both large quantities of concentrates and correspondingly large quantities of costly reagents. Further, the impurities, in particular tellurium were sometimes difficult to remove.
The improvement outlined in the '337 patent was intended to provide a process for the treatment of a by-metal concentrate for 1) to remove troublesome impurities such as Te, As, Bi, Ag, and Pb; 2) the removal of osmium; and 3) to reduce the bulk of the by-metals being refined thereby providing saving in both reagents and equipment. This was accomplished by treating a concentrate of by-metals by heating to between about 1100° C. and 1500° C. in an oxygen-containing gaseous stream for a period of time (examples include times of 20 hours) sufficient to ensure both quantitative removal of one or more of lead, arsenic, silver, bismuth and/or tellurium and the oxidation of ruthenium, rhodium and iridium to their oxides. According to the patent, the oxygen-containing gaseous stream could be air and the exhaust gas could be scrubbed with a liquid to recover osmium. The '337 patent also provided for the separation of ruthenium from the other platinum group metals by fusing the ignited by-metal concentrate with potassium hydroxide and leaching the melt with water to dissolve ruthenium complexes formed during the fusion process. As described in the '337 patent, a by-metal concentrate was heated to about 1300° C. for 20 hours in a stream of air, a process by which osmium, together with lead, arsenic, silver, bismuth and tellurium, were quantitatively removed from the concentrate while less than 10% of the ruthenium and only traces of the other platinum group metals were volatilized. The vapors were scrubbed with a 10% NaOH solution to precipitate all the metals, with the exception of ruthenium and osmium, as hydrous oxides (which settle to the bottom of the receiving vessel). The ruthenium and osmium oxides which are converted to soluble sodium salts according to the following reactions:RuO4+NaOHΠNa2(RuO4)+½O2+H2O  (a)OsO4+2NaOHΠNa2(OsO4(OH)2)  (b)
The ruthenium was then precipitated from the alkali solution by the addition of ethanol to reduce the oxo-anion RuO42− and precipitate the insoluble hydrous oxide (reported as Ru2O3.nH2O but the applicants believe RuO2.nH2O may be more accurate). This precipitate is filtered off together with the sludge in the receiver which contains the other metals which have been volatized and is recycled to the lead alloying stage of the metal process or to some other convenient point if lead alloying is not utilized. The osmium remaining in solution is then precipitated at room temperature as a hydrous oxide (reported as OS2O3.nH2O, but the applicants believe OsO2.nH2O may be more accurate) by acidifying the solution with HCl to a pH of 4.0.
U.S. Pat. No. 4,105,442 (“the '442 patent”) teaches an alternative process for the separation and purification of ruthenium involving the conversion of the ruthenium present in solution to a nitrosylruthenium complex with the ruthenium in the Ru+2 oxidation state. The nitrosylruthenium complex is then converted to a nitrosylruthenium chlorocomplex, which is then removed from solution using a suitable liquid or resin anion exchanger.
The '442 patent notes the existence of conventional techniques for the recovery and purification of ruthenium and osmium based on the formation of low boiling temperature oxides in solution, with the oxides being subsequently removed from the solution by heating. For osmium, oxidation of the metal to the VIII oxidation state is relatively easy, and a number of oxidizing agents can be used. Furthermore, osmium can be efficiently removed as the tetraoxide forms even under fairly strongly acid conditions. In the case of ruthenium however, the oxidation is more difficult and control of the solution pH at a relatively high value is essential. Under these circumstances, removal of ruthenium from solution is incomplete, typically leaving several hundred parts per million of ruthenium in the solution. This not only represents a loss in ruthenium recovery, but the remaining ruthenium constitutes an impurity element during the refining and recovery of the other platinum group metals. Further disadvantages of this process include contamination of the ruthenium distillate with an acid and the explosion danger associated with the highly unstable nature of ruthenium tetraoxide.
Other methods for the separation and purification of ruthenium using solvent extraction and ion exchange methods have met with limited success and usually involve solvent extraction from a nitric acid solution. In such solutions ruthenium occurs as a series of nitrosylruthenium nitrate complexes that can be separated from the solution by solvent extraction with, typically, long chain tertiary amines. It is well known that ruthenium forms a very large number of nitrosylruthenium complexes and that the stability of such complexes is greater for ruthenium than for any other element. Thus, for example, in hydrochloric acid solution the nitrosylruthenium complex RuNOCl2−5 can be formed. This complex is highly extractable, may be formed preferentially, and allows for the separation of ruthenium from the other platinum group metals. This process, however, has its own drawbacks, including 1) the available methods of making the nitrosylruthenium complex typically yield only 90–95% and 2) the other platinum group metals present tend to form complexes that exhibit similar behavior towards anionic solvent extractants.
The '442 patent goes on to address these issues to provide a process for the extraction of ruthenium as a nitrosylruthenium complex with both high yield and selectivity with respect to the other platinum group metals.
Yet another alternative process for the purification of ruthenium metal involved zone-refining. According to this process, a sample of impure ruthenium metal is subjected to one or more heat treatments to form a zone of molten ruthenium, surrounded by solid ruthenium, and move this molten zone along the ruthenium sample and thereby segregate impurities from the ruthenium. Although this technique can produce very pure ruthenium, ruthenium's relatively high melting point (approximately 2280° C.) makes this process very energy intensive and requires more specialized equipment to implement than the applicants' invention.